Unsaturated ester of halogenated alkenes

ABSTRACT

THIS INVENTION DEALS WITH NEW UNSATURATED ESTERS OF A,B-UNSATURATED CARBOXYLIC ACIDS DERIVED FROM HALOGENATED ALCOHOLS OF THE FORMULAS   HO-R-C(-X)=C(-X)-R&#39;&#39; AND HO-C(-X)2-C(-X)2-R&#39;&#39;   WHEREIN R IS A DIVALENT HYDROCARBON MOIETY HAVING AT LEAST ONE AND NO MORE THAN 10 CARBON ATOMS, X IS A MEMBER SELECTED FROM THE CLASS OF BROMINE AND CHLORINE, AND R&#39;&#39; IS A MEMBER SELECTED FROM THE CLASS OF HYDROGEN, X AND A MONOVALENT HYDROCARBON CONTAINING AT LEAST ONE AND NO MORE THAN 20 CARBON ATOMS. TYPICAL ESTERS ARE THE ACRYLATES, METHACRYLATES, MALEATES, FUMARATES, ITACONATES AND CINNAMATES. THESE MONOMERS POSSESS FIRERETARDANT PROPERTIES AND ARE USEFUL FOR THE SYNTHESIS OF POLYMERS AND COPOLYMERS.

3,637,813 UNSATURATED ESTER 0F HALOGENATED ALKENES Gaetano F. DAlelio,2011 E. Cedar St., South Bend, Ind. 46617 No Drawing. Filed Dec. 19,1968, Ser. No. 785,336

Int. Cl. C07c 69/54 US. Cl. 260-486 H .15 Claims ABSTRACT OF THEDISCLOSURE This invention deals with new unsaturated esters ofu,B-unsaturated carboxylic acids derived from halogenated alcohols ofthe formulas wherein R is a divalent hydrocarbon moiety having at leastone and no more than 10 carbon atoms, X is a member selected from theclass of bromine and chlorine, and R is a member selected from. theclass of hydrogen, X and a monovalent hydrocarbon containing at leastone and no more than carbon atoms. Typical esters are the acrylates,methacrylates, maleates, fumarates, itaconates ass cinn amates. Thesemonomers'possess fifel't'aftlafit praperties and are useful ferthesynthesis at polymers and cepol' rners.

RELATED PRIOR ART No pertinent prior art is known. The closest relatedprior art are the polymers containing pendant halogenated acetylenicgroups which are disclosed in J. Polymer Sci., vol. 5, pp. 813-832, pp.999-1014 and pp. 1245-1264 (1967). However this publication does notshow monomers which possess a free vinyl group and a polyhalogenatedethylenic group.

BACKGROUND OF THE INVENTION This invention involves unsaturatedcarboxylic acid esters which contain halogen atoms in their structures.In general, it concerns monoand polycarboxylic acid esters ofpolyhalogenated alcohols. In particular, it deals with a,fl-u11saturatedcarboxylic acid esters of halogenated alcohols of the formulas wherein Ris a divalent hydrocarbon containing at least one and no more than 10carbon atoms, X is bromine or chlorine, and R is H, X or a monovalenthydrocarbon containing at.

least one and no more than 20 carbon atoms.

Typical esters of this invention are the acrylates, the mcthacrylates,the a-chloroacrylates, the B-cyanoacrylates, the maleates, thefumarates, the crotonates, the cinnamates, etc. These typical esters arederivattives of a 3- unsaturated carboxylic acids, all of which containthe essential structure -IF -(IJ-COOI-I (o) By designating thehalogenated alcohols (A) and (B) shown above as ZOH, the new esters ofthis invention can be represented as containing the essential structure3,637,813 ttented Jan. 25, 1972 orncoorr clan-coon, oH.c=ooo0H,NCOH=OHOOOH COOOH 01 01 CH-COOH 1'35 13% needs-e sues, tidbit-:o-coon,CH2=C-C=CH2 CHz CH=-CH CIICOOH, etc. The alt-unsaturated carboxylic acidmay also be dcfined as having the structure,

o=i:oo0t

wherein A and A are each selected from the class con sisting of -H, -X,-CN, COOZ, -(CR' ),,COOZ, and R, preferably at least one A or Arepresenting H. or X; n has a numerical value of 1 to 10; and Z is aradical selected from the class of H,

The esters of this invention are readily prepared. by esterifying theacids A A -Al C O O H l with the alcohols R'CX=CXR-OI-I and byprocedures well known in the art. Instead of the carboxylic acid, thecorresponding acid chlorine or anhydride may be used. When the acidchloride is used, preferably, a hydrohalide acceptor such as a tertiaryamine, as for example, the trialkyl amines, dimethylaniline, pyridine,etc., are used in the reaction:

RaN

P b I --00 01 wax-o x-n-on The ester exchange reaction, using the loweralkyl esters of the above acid, for example,

' i 31:43 0 CH3 or o=oo o o Gin and the alcohol may be used to preparethe new esters of this invention, thus:

The new esters of this invention can therefore be represented by one ofthe formulas:

wherein A, A, R, R and X are as defined above.

Typical divalent hydrocarbon radicals represented by R include etc.

Typical monovalent radicals represented by R include:

etc.

The new esters of this invention are useful with their halogen contentas flame retardants and for the preparation of flame-retardantcompositions. Those esters which contain an activated terminal vinyl orvinylidene group,

are particularly useful for the preparation of homopolymers andcopolymers with other vinyl monomers, including other esters of thisinvention. The new esters of afiunsaturated dicarboxylic esters, such asthe maleates, fumarates are particularly useful for the synthesis ofcopolymers. The esters of this invention find utility not only asmonomers but also as plasticizers and fire-retardant additives to othernon-polymeric as well as polymeric materials. Especially are theysuited, as vinyl monomers, alone or with other monomers, for coreactionwith other unsaturated polyesters, typical examples of which are thepolyalkylene maleates and fumarates, as well as those unsaturatedpolyesters modified by non-olefinic polycarboxylic acids such asphthalic, tetrachlorophthalic, tetrabromophthalic or chlorendicanhydride.

The polymerizable monomers of this invention, as illustrated, forexample, by the acrylate, methacrylates, itaconates, etc., are readilypolymerized or copolymerized to soluble polymers by radical generatinginitiators, such as the peroxides, hydroperoxides, peracetates or byredox systems including hydrogen peroxide with ferrous salts or sodiumbisulfite, potassium or sodium persulfate with bisulfate, etcultravioletlight, ionizing radiation, etc. Radical polymerizations are Well knownin polymer science and are applicable to the monomers of this invention.

The production of soluble polymers, especially from. the new esterscontaining more than one double bond, particularly those having thestructure for example, CH =CHCOOCH CX=CHX, is surprising and unexpectedsince the corresponding allyl esters, CH =CHCOOCH CH=CH and theacetylenic esters. CHFCHCOOCHgCECH, crosslink under radicalpolymerization as shown in J. Polymer Science, vol. 5, pp. 323-337,813-832, 999-1014 (1967). These monomers also differ from thecorresponding allyl and acetylenic esters in that they do not polymerizewith anionic initi ators, since the halogen atoms in the new esters ofthis invention destroy the anionic initiator used. Further, these newesters cannot be prepared directly from the acetylenic ester byhalogenation, since the halogenation is not selective and causeshalogenation, to a great degree, of the vinyl bond in the acid, thusthereby destroying the polymerizability of the original group.

Some of the polymers obtained. by the radical initiation. of certainacrylic and methacrylic esters of this invention, such as CH =CHCOOCHCBr=CHBr and CH2: -C O O CHZC Br=CHBr yield polymers having, at least inpart, repeating units of the formula which repeating units are similarto those obtained by the post-halogenation of the completely linearpolymers obtained by the anionic polymerization of the acetylenic estersof the acrylic acids, as shown in J. Polymer Sci, vol. 5, pp. 813-832,999-1014 (1967). However, the related polymers of this invention,prepared by radical polymerization are not entirely linear polymers,but, as a result of the well-known radical-transfer phenomenon,particularly in systems comprising halogenated compounds, are branchedpolymers. This is particularly advantageous when the polymer is intendedfor use as a fire-retardant additive, since the solution and meltviscosities of branched polymers are notably lower than the relatedlinear polymers of the same molecular weight. This lower viscosityincreases the compatibility of the polymers with other polymers, andallows the use of lower temperatures in processing the polymers ormixtures of polymers. Many of the polymers prepared from the monomers ofthis invention, however, have no relation to the posthalogenatedacetylenic ester polymers mentioned hereinabove. For example, theitaconic ester polymers, and the copolymers of the maleic or lnmaricesters are readily prepared by the radical initiation of the monomers ofthis invention, whereas the esters of itaconic acid, fumaric acid andmaleic acid, etc., cannot be polymerized anionically, and thus areunavailable for post-halogenation as are the acrylic-type esters.

Another major advantage accrues from the use of many of the monomers ofthis invention, particularly with the esters of the at-unsaturatedpolycar'boxylic acid such as the itaconates, maleates, fumarates,citraconates. etc. The only requirement of the esters of this inventionis that at least one of the carboxyl groups of said polycarhoxylic acidis esterified by the alcohol, R-CX=CXROH; the remaining one or morecarboxyl groups may be left unreacted or converted to ester groups ofthe same alco-= hols, R'CX=CXR-OH, or of any other saturated,unsaturated, carbocyclic or heterocyclic alcohol, as for example,methyl, ethyl, propyl, amyl, hexyl, stearyl, benzyl, a-llyl, propargyl,butynyl, fi-N,N-dimethylaminoethyl cy clohexyl alcohols, etc., thefl-hydroxyethyl acrylate, fihydroxypropyl acrylate, fl-hydroxyethylmethacrylate, etc., or converted to an acid chloride, or to amides ofammonia, primary amines and secondary amines, such as methylamine,diethylamine, diethanolamine, cyclohexylamine, allylamine, diallylamine,aniline, -N-methyl aniline, p-aminophenol, m-aminobenzoic acid,anthranilic acid.

When the remaining one or more carboxylic acid groups is converted to anunsaturated ester such as the vinyl, allyl, methallyl, crotyl ester,etc., the new derivative can be polymerized to insoluble, infusiblepolymers.

A few examples of such typical monomers which polymerize to insoluble,infusible polymers are H C CHCH OOCCH CHCOOCH CXflI-IX on, H2o=cncrno oOH=CHC o 0 h--ox=cx1 capo-am o o 0 ornox=ox -on,

aHzCO o onzon=orn 0112:0110 0 0 0112011200 0 on=on-c 0 o orncx=onxotr2=o-orno 0 o CHPCX=OXBJ 0 o o oniorro o o C=CHz one o 0 CH2CX=OHX -ooo CH2(JH=CH2 H 0 O CH2CH=CH2 etc,

The monomers of this invention containing a group, wherein P representshydrogen, methyl, chlorine, bromine, cyano and phenyl, homopolymerizereadily with radical initiation such as by means of a peroxy compound,ultraviolet light or ionizing radiation, whereas those monomers havingsubstitution on the alpha and beta carbon atoms homopolymerize underradical initiation less readily and in some cases not at all, but co=polymerize readily according to their reactivity and selec tiveconstants, 1", and r The homopolymerizations and copolymerizations maybe performed (1) in mass, that is, neat, in the absence of addedsolvents or dispersion media; (2) in suitable organic substances whichare solvents for the monomers as well as the polymers, or which aresolvents for the monomers and not for the polymers, in which cases thepolymers precipitate from the media; or (3) in emulsion systems whichare well known in the art and which comprise an emulsifying agent suchas soaps, synthetic emulsifiers, such as dode= cylbenzene sulfonatesodium salts, sodium sulfodioctyisuccinate and the like, in water. Inthe emulsion systems water soluble radical initiators such as potassiumpersulfate, hydrogen peroxide, sodium per'borate, urea peroxide, etc.,are used alone or in the presence of a redox agent, such as sulfurdioxide, sodium bisulfite, ferrous sulfate, etc.

Thus, the polymers and copolymers of this invention can be prepared bythe vinyl type polymerization by means of radial initiators such as theperoxy and azo catalysts as such. or as redox systems as well as byultra violet and ionizing radiation. Of the azo-type catalysts,azobisisobutyronitrile is a typical example and is usually preferred.The peroxy catalysts are illustrated by stearoyl, lauroyl and butyroylperoxide, but for economic reasons benzoyl peroxide, tertiary-butylperoxide and tertiarybutyl peracetate are selected, but, any of theother well known peroxy catalysts such as cumene peroxide and the likecan also be used.

When solutions of the polymers are desired, they can be obtained readilyby polymerization in a suitable organic solvent or a mixture of organicsolvents such as methyl acetate, ethyl acetate, acetone, methylethylketone, methylisobutyl ketone, benzene, toluene, xylene, dioxane,tetrahydrofuran, chloroform, carbon tetrachlo ride, ethylenedichloride,dibutyl ether, etc. In such cases a solution of 5 to of the monomer inthe solvent is used.

When low molecular weight polymers are desired, the amount of radicalinitiator used may be as high as 3 to 4 percent by weight of the monomeror comonomers used; and the molecular weight may be further controlledby the use of radical chain transfer agents such as chloroform, carbontetrachloride, octyl mercaptan, dodecyl mercaptan and the like. Whenhigh molecular weight polymerization products are desired, thepolymerizations are performed preferably in the absence of chaintransfer agents and only sufficient initiator to overcome the inductionperiod of the system, such as of the order of 0.025 to 0.1% by weight ofthe initiator.

Alternately, the polymerization may be achieved thermally, simply byheating to generate the initiating radicals. The polymerization can beperformed over wide range of temperatures depending upon whether thesystem used is a mass, a solution or an emulsion polymerization andwhether the initiation is by a redox system, ultraviolet or ionizingradiation. With ionizing radiation, polymerization can be achieved attemperatures as low as -40 C., but usually at ambient temperatures. Theredox polymerizations can be performed at (l to 70 C,

and the thermal polymerizations can be performed up to temperatures ofthe order of 75 to C. or higher The new monomers of this invention canbe copolym erized with other vinyl monomers such as the acrylic andmethacrylic esters such as the methyl, ethyl, propyl, hutyl, hexyl,cyclohexyl, dodecyl, etc. esters. In addition to, or in lieuof theseacrylic type esters used in such copolym= erizations, any othercopolymerizable monovinyl or monovinylidene comonomer or mixturesthereof can he used, for example, the vinyl esters, that is vinylacetate, and the monovinyl esters of saturated and unsaturated,aliphatic, monobasic and polybasic acids, and more specifically thevinyl esters of the following acids: propionic, isobutyric, valeric,caprylic, caproic, oleic, stearic, acrylic, methacrylic, crotonic,oxalic, malonic, succinic, glutaric, adipic, suberic, azelaic, maleic,furnaric, itaconic, mesaconic, hexahydrobenzoic, citric, trimesic, etc.,is well as the corresponding allyl, methallyl, etc. esters of theaforementioned acids, acrylonitrile, methacrylonitrile, methacrylicacid, hydroxy propyl methacrylate, etc.; amides such as acrylic amide;itaconic acid nionoesters and diesters, such as the methyl, ethyl,hutyl, allyl esters. the maleic and fumaric acid monoesters, diestersand their amide and nitrile compounds, such as diethyl maleate, maleyldiamide, itaconamide, fumaryl dinitrile, dimethyl fumarate, etc.;ethers, such as methallvl ethyl ether, vinyl ethyl ether, vinyl butylether. allvl prooyl ether, vinyl cyclohexyl ether, cyanuric acidderivatives having one copolymerizable unsaturated group attacheddirectly or indirectly to the triazine ring, such as allyl diethylcyanurate, vinyl diethyl cyanurate; the diene such as butadiene,isoprene, etc.; as well as the partial, soluble or fusible polymerizablepolymers of the hereinahove listed monomers, etc.

Typical suitable aromatic comonomers include vinyl aryl compounds suchas styrene, vinyl naphthalene, vinyl toluene, vinyl xylene, vinylphenol, vinyl ethyl benzene, vinyl dimethyl naphthalene, vinyl diphenyl,etc., chlorostyrenes, etc., vinyl phenyl ether, vinyl benzoate, vinylnapthoate, vinyl methyl phthalate, allyl ethyl phthalate, allyl propylphthalate, etc.

The polymeric compositions of this invention are particularly useful ascoating compositions on all types of substrates, including cellulose inits various forms, such as paper, Wood, paper board, wood board, woodpulp, regenerated cellulose in film or fiber form, laminates of varioustypes including those prepared from fibrous fillers bonded with urea,melamine, epoxy and polyester resins, plaster board, concrete in. itsvarious forms such as slabs, blocks and the like. They may also be usedas impregnants for porous bodies such as the compositions hereinabovenamed, as well as for synthetic and natural sponges, etc. Particularlydo they find use as bonding agents and adhesives for solid, porous andfoamed bodies. They can be used alone or admixed with each other or withother copolymerizable monomers, unsaturated or saturated polymers, inthe absence or presence of dyes, pigments, plasticizers. For coating,impregnating or ad-= hesive compositions where the presence of smallamounts of solvent in the cured composition is not objectionable theycan be mixed with volatile or non-volatile solvents best suited to theparticular application.

The polymers of this invention are also useful in the preparation ofcopolymers with unsaturated alkyd resins. In carrying this portion ofthe invention into effect, an esterification product of a polyhydricalcohol and an alpha, alpha-unsaturated polycarboxylic acid is firstprepared in accordance with techniques now Well known to thoseskilled'in the alkyd resin art, such as ethylene glycol maleate,propylene glycol maleate, ethylene, glycol maleate= phthalate, ethyleneglycol meleate-acrylate, propylene gly colfumarate-methacrylate and thelike.

In many cases, instead of copolymerizing a single monomer of thisinvention with a single alkyd resin, mixtures can be used of two or moresuch monomers with a single alkyd resin, or a single monomer can be usedwith two or more alkyd resins, or a mixture of two or more monomers withtwo or more alkyd resins.

The polymers of this invention can be used alone or with fillers, dyes,pigments, opacifiers, lubricants, plasti cizers, natural and syntheticresins or other modifying bodies in, for example, casting, molding,laminating, coating applications, and as adhesives, impregnants, andprotective coatings.

In preparing copolymers, the monomers of this invention can constituteas much as 98 to 99.5% by weight of the whole, or the modifyingcomonomer or alkyd resin can constitute 98 to 99.5 of the whole.

In general, the proportions of the components used in a particularformulation will depend upon the particular properties desired in theinterpolymer. For most applications, it is preferred to use 20 to 80percent of the monomers of this invention and from 80 to 20 percent ofthe modifying polymer or monomer, since within these rangesinterpolymers best adapted for most commercial applications can beproduced.

Within these ranges the new interpolymers have a wide range ofproperties. For example, depending upon the particular crosslinkingpolymer and any modifying polymer or monomer, the particular proportionsthereof, the conditions of polymerization, such as the temperature,pressure, presence or absence of additives, etc., and the extent ofpolymerization, they can vary from soft flexible bodies to hard rigidmasses of varying resistance to solvents.

For coating or impregnating applications where the presence of a smallamount of solvent in the cured composition is not objectionable, themixed starting component can be diluted with volatile or non-volatilesolvents or diluents best suited for the particular service application,and then can be polymerized after the application of the solution to theparticular article to be coated or im- 8 pregnated, or impregnated andcoated. By suitable selec tion of the starting material and theconditions of inter polymerization, interpolymers can be obtained in anin soluble, infusible state practicall resistant to the destruc tiveeffect of other chemical bodies, such as acid, bases, salts, solvents,swelling agents, and the like.

When it is desired to modify the properties of the cross linkablemonomer of this invention, this can be accomplished by copolymerizing amixture comprising at least one such polymer with at least onecopolymerizable monomer containing at least one unsaturated ethylenic,or acetylenic hydrocarbon radical, more particularly, a CH =C radical,such as vinyl, allyl, methallyl, vinyl idene, etc., or with acopolymerizable compound contain ing a CH:CH, or a CH=C or a C=Cgrouping, for example as in vinylidene fluoride, vinylidene cyanide,vinyl propionate, maleic anhydride, or its esters and amides, methylmaleic anhydride, tetrafluoroethylene, etc.

In preparing copolymers of the crosslinkable monomers with polymerizablecomonomers such as methyl methac-- rylate, styrene,- acrylonitrile, andthe like, the crosslink able polymer can constitute as little as 0.1percent by weight of the whole, whereas in other cases the crosslinkable polymers can constitute as much as 98 to .99 percent of thewhole. The proportion of the components in a particular formulation willdepend upon the partie ular comonomers used and the particularproperties desired in the copolymer. The polymers and copolymers can beprepared most readily by ionizing radiation. p

The acrylic monomers of this invention, particularly those having thestructures are particularly suited for grafting to polymers in fiberform, by techniques Well known in the art to render the fibersnon-burning, such as to fibers or textiles of the nylon, polyvinylalcohol, regenerated cellulose, cotton, etc. They are particularlyuseful in this respect for cellulose fibers and fabric such as derivedfrom rayon or cot ton. One particularly useful method is to form a redoxmetal complex of the acidic cellulose, or, of the reaction product ofcellulose with carbon bisulfide, and to graft the monomer directly .tothe cellulose.

Various methods of practicing the invention are illus trated by thefollowing examples. These examples are in tended merely to illustratethe invention and not in any sense to limit the manner in which theinvention can be practiced. The parts and percentages recited thereinand all through this specification, unless specifically providedotherwise, refer to parts by weight and percentages by Weight.

EXAMPLE 1' One hundred forty-five parts of 1,2,3-trichloropropene areadded to a solution of 106 parts of sodium carbonate dissolved in 900parts of water and the mixture refluxed for ten hours. The water layeris then separated from the oily layer which is dried over anhydroussodium carbonate, separated by filtration and distilled. There isobtained 115 parts of 2,3-dichloro- 2-propene-L01,

ClCH=CClCH OH (I), B.P, 45-46" CD/LS mm: yield, 91%,

EXAMPLE II (a) To 250 parts of carbon tetrachloride is added 56 parts ofpropargyl alcohol (A) and to this solution there is added slowly, atroom temperature, a solution of 160 parts of bromine in 250 parts ofcarbon tetrachloride and allowed to react at room temperature for twohours, then the mixture is heated to 3040 C. for two hours, The mixtureis then distilled to recover the carbon tetrachloride and the2,3-dibromo-2-propene-l-ol,

BrCH=CBrCH OH (II), B.P. 51-52 C./0 7 mm.; yield, 93%.

(b) Treatment of 1,2,3-tribromopropene with aqueous sodium carbonate bythe procedure of Example I yields the same 2,3-dibromo-2-propene-l-oLEXAMPLE III The reaction of 2-methyl-3-butyn-2-ol (B) with NaOCl underan inert atmosphere of nitrogen according to the procedure given in theBull. Soc. Chim. (France), pt 1615 (1965), gives an 87% yield of4-chloro-2-methyl-3-butyl= C 3 ClCEC I-OH CH B.P. 5456 C./18 mm,

EXAMPLE IV 10 butyn-Z-ol,

B.P, 9293 C./22 mm,

20 EXAMPLE v The procedure of Example II(a) is repeated using instead ofpropargyl alcohol, one equivalent weight of the following acetylenicalcohols to obtain the halo-derivative corresponding to the alcoholused:

Aeetylenic alcohol Dlbromoethylene derivative The reaction of2-methyl-3-butyl-2-ol in Water with Br and NaOH by the procedure givenin Ann. Chem, (Rome), 47, 118 (1957), yields 4-bromo-2-methyl'3 1 1 I2TABLE-Cntinued Acetylenic alcohol Dibromoethylene derivativeCeH:CECCHzOH (R) Br Br CsHC= C-CH2OH (XXI) CsH5CEO-CH2CH1OH (S) Br Br(XXII) CnH5=-CH2CH2OH CaHuCEC-CH2OH (T) Br Br (XXIII) CtH11( J=( 1-CHzOHCH3 (U) Br Br CH3 (XXIV) CoH5CECCH-OH CGHIS =C-CHOH CH5 Br Br CH:CuH5CEC-COH CtHsC=C-COH (XXV) H I/Ha CH; (III) Br Br CH3 (XXVI)C1CEC-C-OH C1|C:G OH

CH3 CH3 v (3H2 (1V) Er IIBr CH xxvn) BrCEC-COH BrC=C- OH 3 3 I/HaCioH1CECCH2OH (W) Pf! 1'31 (XXVIII) CloH7C=O-CHzOH EXAMPLE v1 CH3 Br (a)Into a solution of 56 parts of propargyl alcohol and 0.1 part of iodinein 300 parts of tetrachloroethylene is slowly passed chlorine gas whileexposed to an ultraviolet lamp until 70 parts of chlorine are reacted.The halogenated product is then recovered by distillation and themajority of the product is identical to the 2,3-dichloro- 2-propene-1-olof Example I.

(b) In a similar manner there is prepared Cl Br CIQC=CCH OH(XXXIII), andBr2C=(. lCHzOI-I(XXXIV) EXAMPLE VII A mixture of 127 parts of2,3-dichloropropene-l-ol, 86 parts of methacrylic acid, 400 parts oftoluene, 0.50 parts of toluene sulfonic acid and 1. part oftertiary-butyl catechol are reacted at refiux in a Dean-Stark apparatusunder a nitrogen atmosphere until about 18 parts of water are collectedin the trap. Then a saturated aqueous solution of sodium carbonate isadded to the reaction mixture to neutralize the acid, the aqueous layeris separated from the mixture which is again washed with distilledwater, the benzene layer is then separated, dried over anhydrous sodiumcarbonate and filtered. The filtrate is distilled at reduced pressure toremove the benzene and to remove the ester. There is obtained a 93%yield of B. P. 40-41 C./ 0.20 mm. Hg. Analysis for chlorine gives avalue of 41.8% which is in close agreement with the theoretical value.

EXAMPLE VIII The procedure of Example VII is repeated except thatinstead of the 2,3-dichloropropene-l-ol, there is used 200 parts of2,3-dibromopropene-1-ol and there is obtained B.P. 56-57" C./0.15 mm.Hg. Analysis gives a value of 58.8% bromine which is in good agreementwith the calculated value.

EXAMPLE IX The procedure of Example VII is repeated using instead of the2,3-dichloropropene-1-ol an equivalent quantity of 1131' HOCH2C=CBH andthere is obtained the ester,

peated using 72 parts of acrylic acid instead of meth acrylic acid andthere are obtained the acrylic esters,

CH =CHCOOCH CCl=CHCL CH =CHCOOCH CBr=CHBr,

CH =CHCOOCH CBr=CBr and CH CHCOOCH CCl=CCl respectively.

EXAMPLE XI A mixture of 98 parts of maleic anhydride, 127 parts of2,3-dichloropropene-1-O1 and 400 parts of dry benzene are reacted at C.for twenty-four hours and the mixture cooled to 5 C. Crystals of thehalf-ester product are removed by filtration and dried in a vacuum oven.There is obtained 213.8 g. yield) of HOOCCH=CHCOOCH CCl=CHCl which onanalysis shows 31.5% chlorine which is in good agreement with thetheoretical value.

Substitution of an equivalent quantity of 2,3-dibromopropene-l-ol forthe 2,3-dichloropropene-1-ol yields the corresponding ester,

HOOCCH-CHCOOCH CBr=CHBr EXAMPLE XII The procedure of Example XI isrepeated using 112 parts of itaconic anhydride instead of the maleicanhydride and there is obtained the ester,

OH2=COHzC O O CH2C O1=CHCl EXAMPLE XIII To a mixture of 800 parts of drybenzene, 127 parts of 2,3-dichloropropene-l-ol and 101 parts oftriethylamine cooled to 5 C. is added slowly with stirring 148 parts ofmethyl fumaryl chloride, H COOOCH=CHCOCL over a period of one andone-half hours. The mixture is then filtered to remove the triethylaminehydrochloride and hexane is added to the filtrate until itibecomesturbid. The solution is filtered, decolorizecl with charcoal and thesolvent-removed from the filtrate at 15 mm. Hg pressure, leaving as aclear viscous oil, the product H COOCCH=CHCOOCH CCl-CHCl When 174 partsof allyl fumaryl chloride are used instead of methyl fumaryl chloride,there is obtained the ester, H C=CHCH OOCCH=CHOOOCH ClCHCl EXAMPLE XIVThe procedure of Example XIII is repeated using 105 parts of methacrylylchloride instead of the methyl fumaryl chloride and there is obtainedthe methacrylic ester,

r CH2=C.OOOOH2CC1=CHC1 identical to that of Example VII.

Substitution of 95 parts of acrylyl chloride instead of the methylfumaryl chloride of Example XIII yields the acrylic ester, CH =CHCOOCHCCl=CHCL identical to that of Example X.

EXAMPLE xv (a) The procedure of Example VII is repeated using 225 partsof HOOCCH=CH CHCOOCH CCl=CHC1 instead of the methacrylic acid and thereis obtained 297 parts of the ester,

CHCOO CH2OC1=OHOI CHOOOCH2C1=OHO1 (b) When 239 parts of CH2 H0OC(]COOGHzCCl-CHC1 are used instead of the methacrylic acid of Example XV(a), there isobtained 330 parts of the itaconic ester,

' CH2=C-COOGHzCCl=OHCl H2000CH2CO1=OHCI EXAMPLE XVI The followingunsaturated polyesters are prepared, as illustrative of the class ofunsaturated alkyd resins, by heating the ingredients in an inertnitrogen or carbon dioxide atmosphere.

Alkyd resin A-Ethylene glycol m-aleate Parts by weight Ethylene glycol68.2 Maleic anhydride 98.0

.The components are mixed and slowly heated in the course of one hour to190 C. and held at this temperature for four to six hours, until theacid number is reduced to below 40.

Alkyd resin BEthylene glycol-maleate-phthalate Parts by weight Ethyleneglycol 68.2 Maleic anhydride 49.0 Phthalic anhydride a- 74-0 Thecompounds are mixed and heated according to the procedure given abovefor alkyd resin A.

Alkyd resin C Parts by weight Propylene glycol 68.2 Maleic anhydride65.0

Tetrabromophthalic anhydride 140.0

The compounds are mixed and heated slowly to 190 C. and held at thistemperature for three hours, then raised to 200 C. until the acid numberis at least 40 or lower,

EXAMPLE XVII Esterification of alcohols V to XXXIV by the procedure ofExample VII or of Example XIV yields the corresponding methacrylicesters,

EXAMPLE XVIII above, the monomers V to XXVIII inclusive are readilyconverted to the methacrylic and acrylic esters,

EXAMPLE XIX Substitution of 161 parts of the fumaryl amide chloride, (HC) NOCCH=CHCOCl for the methyl fumaryl chlo= ride in Example XIII yieldsthe amide ester,

EXAMPLE XX (a) To 50 parts of CH3 B1 in a glass tube is added 0.5 partsof benzoyl peroxide and the mixture stirred at 25 C. until the radicalinitiator is dissolved; the tube sealed under nitrogen and heated at C.for twenty-four hours and at C. for eighteen hours. There was obtained aclear, almost water-white rubbery polymer. When a sample of the polymeris ignited it does not continue to burn. The polymer is readily solublein chloroform, ethylene dichloride and benzene.

1 5 (b) Fifty parts of is polymerized as in Example XX(a), When ignitedthe polymer continues to burn with difficulty, but when thepolymerization is repeated by first adding 5 parts of trimethylphosphite to the monomer and the mixture polymerized, the resultingpolymer, when ignited, does not continue to burn. In contrast, when amixture of 50 parts of methyl methacrylate and 5 parts of trimethylphosphite is polymerized, the resulting polymer continues to burn whenignited.

(c) Fifty parts of of Example VIII(b) are converted to soluble,self-extinguishing polymers by the procedure of Example XX(a).

(g) The methacrylic esters,

of Example XVIII(b) are converted to soluble, self-extinguishingpolymers by the procedure of Example XX(a).

EXAMPLE XXI (a) A mixture of 94 parts of methyl methacrylate and 6 partsof is copolymerized by the procedure of Example XX(a) and the resultingcopolymer is self-extinguishing when ignited. The copolymer is solublein chloroform, benzene and toluene.

(b) A mixture of 92 parts of methyl methacrylate and 8 parts of iscopolymerized by the procedure of Example XX(a) and a self-extinguishingcopolymer is obtained.

EXAMPLE XXII The procedure of Example XXI(b) is repeated six times usinginstead of methyl methacrylate, 92 parts of each of the following:methylacrylate, styrene, acrylonitrile, vinyl acetate, beta-cyano-ethylmethacrylate, vinyl chloroacetate, and in all cases Self-extinguishingpolymers are obtained.

1 6 EXAMPLE XXIII (a) To each of 50 parts of alkyd resins A, B and Crespectively are added 50 parts of and 0.20 part of tertiary butylhydroperoxide; then fiberglass mats are impregnated with these solutionsaccording to procedures Well known in the art to 45% resin contents. A3-ply laminate is prepared and placed between two layers of polyethylenefilm and cured for two hours at C. and "four hours at C. The curedlaminates when tested for flame-resistant properties by A.S.T.M. MethodD63 5-44 are found to be non-burning and self extinguishing.

(b) The procedure of Example XXIII(a) is repeated but 30 parts of the isreplaced in four separate tests by 30 parts styrene, methylmethacrylate, vinyl acetate and triallyl cyanurate respectively, and inall cases non-burning, self-extinguishing laminates are obtained.

and in all cases, self-extinguishing, non-burning laminates areobtained.

EXAMPLE XXIV To 100 parts of CH =CHCOOCH CCl=CHCl there is added at roomtemperature one part of AlCl and a dark-brown, almost black colored gelis obtained with the elimination of HCl.

EXAMPLE XXV The following mixtures are first prepared:

Parts (A) Methylmethaerylate 76 CHi CH 2t CHpr-CO O -CBr=CHBrBenzophenoue 0. 2

(B)..... Methylmethacrylate 75 CH3 B1 20 CH;=(EO 0 O CHaCBr=( J 01 CHCH3 4 ()Hp-C O O CHgCHzO 0 G JJ=CH Benzophenone 0. 1

and then irradiated with ultraviolet light from a IOU-watt mercury lampuntil the mixture becomes solid. In both cases, self-extinguishingnon-burning copolymers are obtained. Copolymer (B) is insoluble andinfusible due to the crosslinking monomers.

17 EXAMPLE XXVI Parts (A)..... om=onoooomonr=ornzr 20 5 on, so orrFo-oo0 on,

om=onoo o CH CHOH2OOCHC=CH 20 (B)----- CH: CH; 20

oHl=oo00( J-o1ar=0HBr H8 (CH2=CHC00 onzon-omootnnlownm 10 CH; 50 capo-000 on,

(0)..... om=onoooonlooi=ono 15 ro onzosl=omsm 10 on, 5 cape-000mm,

on, 20 capo-o o 0 can on oooo 70 (D)..... Alkyd resin B 50CHzOHCOOCHzCBr=CHBL a0 CH3 1U 5 on,=o c 0 oomorr-cm i H H n on, som=onomoooon=onoooo oaponnr 40 I C Ha (E)..... CHz=CH-COOCHiCCl=CHCl 201= oomoH=om), 20

(CHz=CHCOQCH2)z o Samples of mixtures (A), (B), (C), (D) and (E) areplaced in glass vials which are swept out with nitrogen and sealed, andthen exposed to the beam of a 1 mev. van der Graaf accelerator andinsoluble, infusible, non-burning, self-extinguishing: polymers areobtained at dosages varying from 4 to 10 megarads. Similar results areobtained when other sources of ionizing radiation are used, such as fromnatural or synthetic radioactive material, for example, from Cobalt 60or from the Varian type travelling wave linear accelerators or the typesof accelerators described in U.S. Pat. 2,763,609 and British Pat.762,953.

When 20 ml. wood ply is impregnated and saturated with the mixtures (A),(B), (C), (D) and (E), and then covered with 0.1 ml. polyethylene sheetand irradiated to 6 megarads as above, and the polyethylene barriersheet removed, the resulting cured, impregnated wood is found to bedense, water resistant, self-extinguishing and nonburning.

EXAMPLE XXV II A skein of 40 parts of cotton thread is placed in 1000parts of an aqueous solution containing parts of NaOH, 5.0 parts of CSand 0.10 part of sodium dodecyl'benzenesulfonate and allowed tostand for30 minutes. hTe skein is then removed, washed thoroughly with distilledwater and immersed in 1000 parts of solution containing 0.2

18 part of FeSO -(NH SO and 3.0 partsof tetra-bis-hy-= droxymethylphosphonium chloride for 10 minutes. The skein is then washed withdistilled water and suspended in 2000 parts of an emulsion containing 24parts of 0.2 part of sodium dodecylbenzenesulfonate and 3.0 parts ofhydrogen peroxide and the mixture heated with agitation at 60-70 C.under nitrogen for 3 hours following which the skein is removed, washedwith water and dried. There is obtained 62.71 parts of grafted threads,which when suspended and the ends ignited, are self extinguism ing whenthe source of flame is removed.

While certain features of this invention have been de= scribed in detailwith respect to various embodiments.

thereof, it will, of course, be apparent that other modifications can bemade within the spirit and scope of this invention and it is notintended to limit the invention to the exact details shown above exceptinsofar as they are defined in the following claims.

The, invention claimed is:

1. The unsaturated halogenated ester having a formula selected from theclass consisting of R is a divalent hydrocarbon radical having 1-10carbon atoms therein; I

R is H and monovalent hydrocarbon radicals of 1-20 carbon atoms; 1

X is bromine or chlorine; and

A and A each represent R.

x x cHi=oooooRo=o1v 8. The ester of claim 1 having the formula 0 H, x xoHl= 5-0 oon-(a =on' 9. The ester of claim 1 having the formula CH=CHCOOCH CX=CHX 10. The ester CHFCHCOOCH CBFCHBL 11. The ester of claim9 having the formula CH,===CHCOOCH:CC1=CHC1 12. The ester of claim 9having the formula CH CHCOOCH CBr=CHBr 13. The ester of claim 8 havingthe formula 19 20 14. The ester of claim 1 in which either A or A isLORRAINE A. WEINBERGER, Primary Examiner methyl and the other of the twois hydrogen.

15. The ester of claim 1 in which both A and A are KILLOS AsslstantExamm" methyl. Us. 01. X.R.

R f d 5 106-15 PP; 117 140, 145, 148, 155; 161-231, 247, e 249, 250;204-15922; 252--8.1; 260-13, 30.4, 31.2, UNITED STATES PATENTS 32.8,33.2, 33.6, 33.8, 45.85, 47, 75, 78, 83.5, 85.5, 86.1, 3,151,183 9/1964Billet a1 260-485 X 86-3, 86-7, 9.5, 465.7, 476 R, 4

3,316,329 4/1967 Waples 260-486 X UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTWN Patent No. 3,637,813 Dated v January Z5 1972Inventor(s) Gaetano F. D'Alelio It is certified that error appears inthe above-identified patent and that said Letters Patent are herebycorrected as shown below:

Correct the formula in Claim 7 to read:

a I CH2=CHCOORC=CR' Signed and sealed this 26th day of September 1972,

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents

